Azo pigments of the aminoanthraquinonylazo-hydroxynaphthoic acid series

ABSTRACT

Azo pigments of the formula WHERE A is an aminoanthraquinone, R1 and R2 are substituents and B is hydrogen, alkyl, aralkyl, aryl or heteroaryl, which are useful for dope dyeing, for print pastes for printing, for production of colored surface coatings, for dyeing phenoplasts, aminoplasts or thermoplasts, for textile printing, and in high grade printing inks. These pigments are particularly suitable for coloring polyvinyl chloride, polyethylene or polypropylene with excellent fastness to light, migration and overcoating.

United States Patent 1 Ruider et a1.

[11] 3,821,191 [451 June 28, 1974 AZO PIGMENTS OF THEAMINOANTHRAQUINONYLAZO- HYDROXYNAPHTHOIC ACID SERIES 21 Appl. No.:204,310

. 52 us Cl 260/l52,8/4, 106/23,

106/288 Q, 106/300, 106/308 N, 106/311, 117/123 C, 117/1388 R, 117/1388PV, 117/1388 E, 117/139,117/143 R, 117/147, 117/154, 260/37 R, 260/41 C,260/154, 260/165, 260/155, 260/202, 260/256.4 Q, 260/287 R, 260/326 A,260/326 D, 260/326 N [51] Int. Cl...... C09b 1/16, C091) 21/36, D06p1/44 [58] Field of Search 260/152, '154, 155, 156, 260/165 [56]References Cited UNITED STATES PATENTS 1,758,313 5/1930 Eckert et a1.260/152 3,356,672 12/1967 Schefczik 260/152 3,402,166 9/1968 Heck] eta1. 260/152. 3,468,872 9/1969 Schefczik et a1 260/152 3,509,122 4/1970Horstmann et a1. 260/157 3,513,153 5/1970 Horstmann et a1. 260/1523,600,374 8/1971 Mory 260/152 3,627,748 12/1971 Roueche et a1 260/1523,634,388 l/1972 Horstmann et a1, 260/152 3,644,405 2/1972 Horstmann eta1. 260/156 3,699,126 10/1972 Peters et al.; 260/3292 PrimaryExaminerFloyd D. Higel Attorney, Agent, or FirmJohnston, Keil Thompson &Shurtleff 57 ABSTRACT Azo pigments of the formula where A is anaminoanthraquinone, R, and R are substit'uents and B is hydrogen, alkyl,aralkyl, aryl or heteroaryl, which are useful for dope dyeing, for printpastes for'printing, for production of colored surface coatings, fordyeing phenoplasts, aminoplasts or thermoplasts, for textile printing,and in high grade printing inks. These pigments are particularlysuitable for coloring polyvinyl chloride, polyethylene or polypropylenewith excellent fastness to light, migration and overcoating.

2 Claims, N0 Drawings 2 AZO PIGMENTS OF THE AMINOANTHRAQUINONYLAZO-HYDROXYNAPHTHOIC ACID SERIES The invention relates to dyes having thegeneral formula: CH3

fi or i o bl N OH R in which R has the meanings givenabove. I

NHOO D es of the general formula (1a) CONH N43 y A 2 I 1 9? I in which rA denotes the radical of a l-aminoanthraquinone or OH NHCOZ-aminoanthraquinone which may bear chlorineas 30 I 1 a substituent inthe 3-position or 4-position or of g CONH X 2,4,5-trichloroaniline; 4 Rdenotes hydrogen, chlorine, bromine, alkyl, alk- W M A v I 7 a oxy,methylsulfonyl, cyano, carbamoyl, N- i arylcarbamoyl or carboalkoxy; inwhich R denotesihyd'rogen, chlorine, bromine, alkyl, alk- R denotes y rg ne.:cyano. me hyl O meoxy or carboalkoxy; and thoxy;

} -B denotes hydrogen, unsubstituted or substituted R denotes hydrogeChlorine, m t y or m y; and alkylor aralkyl, or aryl having one to threerings which may bear substituents and which may have B denotes phenyl ornaphthyl which may bear chloring heteroatoms; and rine, methyl, ethyl,methoxy, ethoxy, phenoxy,

the NHCO groups in formula (I) are in metabenzoyl, phenyl, carbomethoxy,carboethoxy, cy-

position or para-position to each other. ano, sulfonamido, carbamoyl, N-

In addition to the individual meanings of R and R phenylsulfonamido orN-phenylcarbamoyl as subalready specified, they may denote ethyl, ethoxyor carstitutents, or a radical of the formula:

boethoxy and preferably methyl, methoxy or carbomei CH2 thoxy. I

Examples of N-arylcarbamoyl radicals for R are N- X phenylcarbamoyl, andN-phenylcarbamoyl or N-naph- Y thylcarbamoyl bearing chlorine, bromine,phenyl, met- 40 hyl, methoxy, carbamoyl, sulfonamido, carbomethoxy orcyano as substituents.

The radical B may denote (apart from hydrogen):

methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tand A has themeanings given above are of special inbutyl, B-hydroxyethyl, benzyl,phenylethyl, phenyl, and dustrial interest. A-is preferably ananthraquinone radiphenyl, naphthyl or anthraquinonyl bearing fluorine,cal and particularly a l-aminoanthraquinone radical. chlorine, bromine,methyl, ethyl, isopropyl, trifluoro- Dyes having the formula (la) inwhich R and R are hyme thyl, methoxy, ethoxy, phenoxy, chlorophenoxy,drogen are particularly easily accessible.

For the production of the new dyes,

phenyl, benzoyl, cyano, carbomethoxy, carbamoyl, sul- -a. a carboxylhalide of the formula (2):

fonamido, acetoxy, benzoyloxy, methylsulfonyloxy, phenylsulfonyloxy,tolylsulfonyloxy, methylsulfonyl, methylmercapto, acetylamino,benzoylamino, chlorobenzoylamino, methylbenzylamino or nitro assubstituents and the radicals of the formulae:

( b Y (L in which Hal denotes chlorine or bromine may be condensed withan amine of the formula (3):

or b. the diuzo compound of an amine of the formula (4) A NH (4) may becoupled with a coupling component of the formula (5):

The azo dye carboxylic acids on which the azo dye acid halides (2) arebased may be prepared by a conventional method by coupling a diazoniumsalt of the amine (4) with ,B-oxynaphthoic acid.

Conversion of the azo dye carboxylic acid into the acid halide may becarried out in a'conventional way by treating it with chlorinating orbrominating agents such as POCI PBr SOCl or COCl preferably in an inertsolvent such as nitrobenzene, chlorinated benzenes, xylenes, orN-methylpyrrolidone with an addition of a catalytic amount ofdimethylformamide or pyridine.

Examples ofamines of the formula (3) with the NH groups in themeta-position or para-position to the -NHOC group are:

- coy HZNQQ-NHOCQCO/N-Q boon . oca

I GO

2 NHOC-EXCO/N 2 mos )m C1 cow H N-G NHOO-QiC co 2 '-NHOC-:

' C1 co H ng-Moog:

420001; ME 3 can 01 3;} E i 2 n00 Q u a OCH3 CQ\ -NHOCQ Q it OCH.

OCH

conn

H N ==NHOC The condensation of the azocarboxylic acid halides of formula(2) with the amines of formula (3) is advantageously carried out byheating in an organic solvent such as o-dichlorobenzene, nitrobenzene,methyl benzoate, xylene, dimethylformamide or N- methylpyrrolidone andit is also possible to add an acidbinding agent such as sodium acetateor pyridine or a catalytic amount of a compound such as collidine or.N-methylpyrrolidone which accelerate the acylation reaction attemperatures of more than 100C.

7 In the case of sparingly soluble amines of formula (3) it isadvantageous to dissolve them in just a sufficient amount ofN-methylpyrrolidone or dimethylformamide v and then to use this solutionfor the reaction with, the azocarboxylic acid halide of the formula (2)which may be dissolved for example in o-dichlorobenzene.

The coupling components of the formula (5) may be prepared for exampleby condensation of 2- hydroxynaphthalene-3-carboxylic acid chloride withamines of the formula (3) in the presence of a chloriadjusted by addinga buffer such as sodium acetate) and the addition of wetting ordispersing agents, for example aralkyl sulfonates, make for a uniformcourse of the reaction. The new dyes may also be prepared by themodified process of French Pat. No. 1,537,423.

The pigments of the invention are obtained in a very pure chemicalcondition, but occasionally not in the optimum physical form for allapplications. By conventional measures such as size reduction, saltgrinding or recrystallization they may be brought into a form adapted tothe particular application. The new pigments may be used for the dopedyeing for example of viscose, for the production of colored printpastes for book printing or offset printing, for the production ofcolored surface coatings, for example nitrocellulose lacquers, acrylatelacquers, melamine resin lacquers or alkydresins, for dyeing phenoplastsor aminoplasts, thermoplastics such as polystyrene, polyolefins orpolyvinyl chloride, rubber or silicone resins, laminate papers orboards, and for textile printing.

The new pigments are particularly suitable for coloring polyvinylchloride, polyethylene or polypropylene and also in surface coatings andhigh grade printing inks.

The invention is illustrated by the Examples in which the parts (unlessotherwise stated) and percentages are by weight. Temperatures are givenin C.

EXAMPLE 1 216 parts of the dye obtained by coupling diazotized l-aminoanthraquinone with 2-hydroxynaphthoic acid- 3 is heated with 1,300parts of o-dichlorobenzene, 195

parts of thionyl chloride and 5 parts of dimethylform-- amide for 5hours at 110 to 120 while stirring.

After the reaction mixture has cooled, the uniformly crystalline azo dyemonocarboxylic acid chloride is isolated by suction filtration, andwashed with 200 parts of o-dichlorobenzene, then with 600 parts ofbenzene and then with 1,000 parts of cyclohexane. After drying at 80 atsubatmospheric pressure, 178 parts of a red crystal powder is obtained.

Analysis:

dichlorobenzene and then 24.9 parts of finely pow- @jC 0 HN- NHO C KN OOO 430 001-13 dered amine of the formula:

oo COOOH:

and 5 parts of dimethylformamide are added and the whole is heated for 5hours at to After cooling to 80, the precipitated sparingly solublepigment is suction filtered,- washed with a littlehot 0- dichlorobenzeneor cold dimethylformamide and then with cold methanol until the filtraterunning away is clear.

To improve the pigment it may be boiled in methanol or another solventor stirred at room temperature. After drying at 80 at subatmosphericpressure, 32.0 parts of red powder is obtained which is practicallyinsoluble in the usual solvents. Polyvinyl chloride film and sheetingand also surface coatings are colored red shades of excellent fastnessto light, migration and overcoating.

The pigment has the formula:

calculated: found:

Analysis:

Other monoazo pigments are obtained with the components in the followingTable by coupling 1 mole of the diazo compound of an amine specified incolumn 1 with 1 mole of 2-hydroxynaphthoic acid-(3), converting theresultant monoazo dye carboxylic acid obtained into the acid chlorideand condensing it with 1 mole of the amine specified in column 11.

g g 5 Column 111 indicates the shade of a lacquer coating T preparedwith the pigment obtained:

Example I II In GO 2 O Bluish red.

ll HzNQ-NHOC c0 OOCH:

1 NH: O

' h 3 a e as a ov Yellowls red- 6 "do u Q HzN NIIOC- N... um- NTIOC- c 0HzN NH0 0-- 13 V. Same as above B lulsh ml.

Yel lowish red.

Rat 1.

Rod.

14 do C0 D0.

. I-IzN-N n 0 oat-E 15., do t C 0 lVlolet.

mN- NHOC 16 do I I t Red.

o o\ HN NHOC- 17 do Bluish red.

' CO v HzN NHOC- t c0 Y I EXAMPLE l8 "30 After drying at subatmo sphericpressure at 80 29.0

22.0 parts of the azo dye carboxylic acid chloride obtained according toExample 1 is heated in 780 parts of dry o-dichlorobenze ne at about 80.Then a hot solution of 23.2 parts of the amine of the formula:

i I C O l N II N 55 found:

parts of a red powder isobtained which is practically insoluble in theusual solvents. Polyvinyl chloridefilm and sheeting and coatingcompositions are colored therewith red shades of excellent fastness tolight, mi-

35 g'ration and overcoating. Y

The pigment has the formula;

II o in 200 parts of N-methylpyrrolidone-(Z) or dimethyl- Analysis:calculated:

Other monoazo pigments are obtained with the components-of the followingTable by coupling 1 mole of g the diazo compound of the amine specifiedin column I with 1 mole of Z-hydroxynaphthoic acid-(3), converting themonoazo dye carboxylic acid obtained into the acid chloride andcondensing it with 1 mole of the amine specified in column ll.

Column [1] indicates the shade of the lacquer coating 65 prepared withthe pigment obtained.

Exampl If. Ni; V

CO I A v Q- QI I QQ red N-Q-NHOC CO/ brown red OCH ' co NHOC-@ 3 orangeyellowi N OCH red H N--m1oc: Q 5

Dames CO red H N OCH bluish red c oooH I brown red coocn c ooca if I Nred B N300 I co v ' I red 2 'NHOC-:

' bluish v so co 1 H N-Q-NHQCQ blulsh red 00 Q 7 'llowi sh v ye z -mwciiwblulsh red H N NHOC-: 6

piI -Q red 7 co v \N red --mxoc-: l

CO\N c1 red.

co. v. V V CH red .&

Q 01 ex I v iblui sh red;

1 bluish red. I H N--NHOC-: {5

7 00--.- .H N- -NHOC -Q-QCH' bluish red I OCH OCH- 'co 1 N 4303 bluishred 2 1 3 1 co I .H 'N--NHOO-EI '-Of-Q bluish rad 3 3.63 bluish red 1 co112N- -NHQC.@QCO)1Q'GI- red brown -01 d H NNHOC-@ m 1 011 I I 2 5' 00 mH N--m1oc-@ red O: :0 I I N I co Y n u-m1oc-: o Q 0. red 8R2):

' yellowish red 1 CO H N-Q-NHOGQ: N Q bluish red com I Z cox red Cl!red.

' @K --Nnoo u co H N--NHOC-@ red I o co 1 N 1 bluishred HZN'NHOCQOQ/ Qon. co

5 N c1 d 'G B Qi blulsh re v COHN N red z gmaw I c HZN-QW bQ l 1 3 co 7C1 1 I red 6on co 2 Q -KX D Q violet I CN I red co. 1 a u-mloc-m bluih rI an HZN-NHOCQ:CO)Q

1 ca on;

n n-gmioc-gfi 00 I k j? H nr-g-maoc-[l co 13 red red

redv

red C red red

red

brown ra d red red

K -QQQOCQ:

2* d C0 c0002 V cm Z Q' O 00 cu co 3 I co n nmnocm g v cox v N N @MlOCEZ00/ r I red red

chestnut red red

red

red

red

chestnut chestnut f red

2. A dye as set forth in claim 1 in which R1 denotes hydrogen, chlorine,cyano, methyl or methoxy; R2 denotes hydrogen, chlorine, methyl ormethoxy; and B denotes phenyl or naphthyl or phenyl or naphthylsubstituted by chlorine, methyl, ethyl, methoxy, ethoxy, phenoxy,benzoyl, phenyl, carbomethoxy, carboethoxy, N-phenylsulfonamido orN-phenylcarbamoyl or a radical of the formula: